European Journal of Organic Chemistry

The kinetics of the reactions of the anions of ethyl arylacetates with quinone methides and diethyl benzylidenemalonates were investigated in DMSO solution. The resulting rate constants follow the linear free-energy relationship lg k₂ = s_N(N + E), which allowed us to derive their reactivity parameters N and s_N.

Treatment of arylphosphorus acid amides with alkali metal solutions in liquid ammonia results in dearomatisation of the arene fragments and formation of (cyclohexa-1,4-dien-3-yl)phosphorus acid amides. Diarylphosphinic amides tend to undergo Birch reduction of two arene fragments to form bis(cyclohexadienyl)phosphinic amides.

The ring-opening alkynylation of cyclopropenones with terminal alkynes is catalyzed by palladium–N-heterocyclic carbene (NHC) complexes to provide alkenyl alkynyl ketones. In contrast, [3+2] annulation to give cyclopentenones occurs if secondary propargylic esters bearing an aryl or alkenyl substituent are used.

The nucleophilic substitution of a 3,5-dichloro-BODIPY derivative with several polyazamacrocycles was investigated. By controlling the BODIPY/macrocycle ratio, some monomeric and dimeric species could be obtained. The photophysical properties of the compounds were studied as was the influence of different cations for one system.

The zwitterionic aza-Claisen rearrangement of optially active N-allylpyrrolidines and α-phenoxyacetyl fluorides proceeds with complete internal and complete 1,2-asymmetric induction to generate a new C–C bond adjacent to a chiral C-N-Boc functionality. The resulting γ,δ-unsaturated amides serve as key chiral intermediates for the total synthesis of pyrrolizidine alkaloid derivatives.

We report the modular synthesis of bis-oligobenzamides and bis-oligopyridylamides as double-helix peptidomimetics with a variety of spacers in which the disposition of strands is tuneable to mimic a range of super-secondary structures.

Oleocanthal, a component of extra virgin olive oil, possesses anti-inflammatory activity and inhibits the formation of neurofibrillary tangles. In this paper, we have achieved the shortest synthesis of (±)-oleocanthal reported so far from easily available starting materials. Chiral chromatographic resolution of the mixture provided both enantiomers for biological studies.

The formation of amides through the in situ activation of carboxylic acids with [Et₂NSF₂]BF₄ is presented. A wide range of carboxylic acids and amines were used to produce the corresponding amides in up to 99 % yield. The reaction with hindered amines was also possible under slightly modified conditions. An enantiopure carboxylic acid and amine were shown to react without racemization.

Myrtucommulone A (1) is a phloroglucinol derivative that is isolated from myrtle (Myrtus communis) and shows antibiotic, anti-inflammatory, and apoptosis-inducing activities. For pharmacological and racemization studies, we synthesized (+)-1 enantioselectively with an ee value of 70 % in two steps from isobutyryl phloroglucinole, isobutylidene syncarpic acid (4), using first (S,S)-8 and then (R,R)-8.

The synthesis of symmetrical unsaturated diesters of types A–C, obtained from primary, secondary, and tertiary diols derived of dimethyl (+)-tartrate and galactaric acid, is reported. Of the four methods tested, the best was the reaction between the diols and unsaturated acid chlorides in the presence of nBuLi in diethyl ether at –50 °C; this approach affords the diesters in an average yield of 78 %.

A diastereoselective synthesis of isoindole-fused diazacyclooctaindenone derivatives has been accomplished through tandem ring-opening and ring-closing of spirochromene derivatives triggered by different aliphatic 1,2-diamines.

A two-step route involving Wittig reaction followed by tandem reductive cyclization–lactamization is presented for the synthesis of 6H-Isoindolo[2,1-a]indol-6-ones.

Starting from per-substituted 3-amino-4-nitrothiophenes with a 2-chloro- and a 5-vinylsulfanyl substituent the formation of vinyl-S-oxides and subsequent substitution against nucleophiles is reported. Additionally, dehalogenation of the formed halothiophenes is possible with three different methods, which lead to selective dehalogenation at the 2, 5 or 2 and 5 position.

Chirality transfer from the cholestanic backbone of bile acid derivatives to the flexible 2,2′-binaphthyl-1,1′-diylphosphite moiety was obtained in the synthesis of three different phosphite ligands.

Because of facile acyl migrations, the synthesis of enantiopure 1(or 3)-acyl-sn-glycerols is much more difficult than their seemingly very simple structures may imply. Even assessment of their optical purity is a difficult task because of the lack of a feasible means of analysis. Now, new findings have changed everything.

Ynol ethers can be directly obtained under mild conditions by reaction of KOR with β-substituted 2(-p-tolylsulfonyl)acetylenes. Only arylacetylenes (with KOtBu) and TIPS-acetylenes provide good yields of alkyl ethynyl ethers

Propargylallenes offer varied reactivity patterns arising from the presence of two different multiple bond linkages, either separately or in concert. We review their syntheses, structures, rearrangement mechanisms and synthetic utility, together with their behaviour on treatment with transition-metal reagents such as gold(I), silver(I), platinum metals or metal carbonyls.

A practical and modular approach to obtain 17-membered macrocyclic compounds through an intramolecular Heck reaction is reported. These macrocycles contain two contiguous stereogenic hydroxy functional groups and an amino acid moiety in the macrocyclic ring skeleton. The macrocycles were then screened against a zebrafish assay to determine the antiangiogenesis activity of these small molecules.

A modular approach to explore the macrocyclic chemical space around an aminoindoline scaffold is developed. This is achieved by incorporating an amino acid moiety and subsequent “stitching technology”. Through screening of a zebrafish assay, several antiangiogenesis agents are identified.

A general method for the vicinal dioxygenation of enecarbamtes is developed by using PhI(OAc)₂ as the oxidant. The reaction is carried out without the assistance of a transition metal under mild conditions to afford β-oxy-α-amido ethers in good yields. Nu = nucleophile, LA = Lewis acid.

The preparation of potassium (1-organo-1H-1,2,3-triazol-4-yl)trifluoroborates from potassium ethynyltrifluoroborate and alkyl or aryl halides by employing a regioselective one-pot Cu-catalyzed azide–alkyne cycloaddition (CuAAC) is elaborated. This strategy allows unrestricted access to an infinite variety of 1,4-disubstituted 1,2,3-triazoles.

A two-step protocol for the synthesis of 4,6,7,8,8a,9-hexahydropyrrolo[1,2-a][1,2,3]triazolo[1,5-d]pyrazines was developed. The first step is an AuBr₃-catalyzed three-component coupling of aldehydes, alkynes, and an amine to give propargylamines under solvent-free conditions at 80 °C. The second step is the ring-closure to give the final products under mild reaction conditions.

A highly regioselective synthesis of 5-substituted 3-aminoisoxazoles has been achieved by a one-pot three-component coupling of β-oxo dithioesters, amines and hydroxylamine in ethanol at reflux via an in situ generated β-oxo thioamide intermediate. The mechanism of the reaction has been established experimentally and shown to be in agreement with the HSAB theory.

Benzyloxycarbonyl-protected hybrid hydrazino dipeptides and benzyloxycarbonyl-protected hydrazino aminoacyl conjugates with N-, S-, O-, and C-nucleophiles were prepared by using benzotriazole methodology.

The enantioconvergent conversion of racemic allyl indolenin-3-carboxylates into enantiomerically enriched C3-quaternary indolenines is reported. A Pd-catalyzed decarboxylative allylic alkylation reaction is employed for both stereoablation and enantioselective formation of the quaternary carbon center.

Cycloaddition of azide with a bisalkyne chemoselectively forms a triazole, which subsequently undergoes oxidative cleavage by atmospheric oxygen to yield a carboxylic acid and an aldehyde. The mechanism for this reaction is investigated in depth.

Strategically divergent: Designing synthetic pathways from pluripotent intermediates. Getting more molecules for your carbon.

The 7-azabicyclo[2.2.1]heptane skeleton was exploited to achieve a new approach to the syntheses of enantiomerically pure cis-1,2-cyclohexanediamine derivatives and conformationally rigid 7-azabicyclo[2.2.1]heptan-2-amines. This was achieved on a multigram scale without producing the undesired diastereomers.

A new route to 6(5)-bromo-5(6)-methylimidazo[1,2-a]imidazolin-2-ones have been developed. A novel and effective strategy of functionnalization of these scaffolds throught Suzuki–Miyaura cross coupling reactions is reported. Thanks to this methodology, a large panel of boronic acids were easily introduced, giving access to a diversified library of 6(5)-substituted 5(6)-methylimidazo[1,2-a]imidazolin-2-ones.

Almost forgotten: The Paulsen acetoxonium rearrangement provides a facile and rapid access to rare carbohydrates. Through a cascade of antimony pentachloride induced acetoxonium rearrangements, ido- and talopyranose derivatives can be synthesized from simple glucose and galactose precursors in a one-pot procedure.

The direct addition of alkyllithium and Grignard reagents with β-hydrogen atoms to fulvenes has been dogged with the problem of competing hydride transfer. Copper catalysis overcomes this and allows access to titanocene dichlorides with high anticancer activity.

Rigid, flexible, rigid: the combination of a 3,4-disubstituted oxazolidin-2-one ring, a flexible methylene group and a 1,4-disubstituted triazole ring allows the formation of a new dipeptide mimic that favours the formation of bent conformations.

Recipe for β-Sheets: Combine one N-methyl-amino acid, two δ-linked ornithine turn units, and nine α-amino acids by solid-phase peptide synthesis. Cyclize in solution, deprotect, and purify by RP-HPLC. Confirm folding by ¹H NMR ROESY and magnetic anisotropy studies. Serve to laboratories interested in studying and inhibiting amyloid aggregation or studying β-sheet assembly.

The three-component synthesis of polysubstituted pyridines starting from 1,3-dicarbonyl compounds, α,β-unsaturated carbonyl derivatives and ammonium acetate has been studied, including the scope and mechanism. This methodology is a rare example of a totally regioselective multicomponent access to highly substituted pyridines that complies with many of the stringent criteria of sustainable chemistry.

In contrast to N-tosyl-substituted 3-alkyl-2-(tert-butyldiphenylsilylmethyl)azetidine, the corresponding 3,3-dialkyl derivative rearranges into N-tosyl-2-alkenyl-3-(tert-butyldiphenylsilyl)amine upon exposure to BF₃·OEt₂. The reaction involves sequential σ_C–N bond cleavage, 1,2-migration of the N-tosyl-aminomethyl group, and deprotonation of the resultant tert-carbenium ion.

A mild and selective method for radioiodination of aromatic compounds is described. This method is used to label three regioisomers of an analogue of griseofulvin with potent anticancer activity. The method takes advantage of the ipso-directing effect of a trimethylsilyl (TMS) substituent and is also demonstrated to work for the local anesthetic lidocaine.

The formation of C₁₂-helical structures in the hybrid αγ oligopeptides Boc–[Aib–γ⁴(R)Val]_n–OMe in solution is demonstrated by NMR and IR methods. The intramolecularly hydrogen-bonded solution conformations resemble those previously determined by X-ray crystallography. C₁₂-helix development has also been monitored by far-UV CD.

A sensitized, intermolecular [2+2] photocycloaddition of maleic anhydride and N-protected 3-pyrroline is the key step in the synthesis of azabicyclo[3.2.0]heptane derivatives. Thus, new γ-aminobutyric acid analogues with a carboxy function in the 6-position, either with or without an additional functional group in the 7-position of the azabicyclo[3.2.0]heptane skeleton, were synthesized.

The application of o-nitrobenzyl (oNBn) ether as an arming participating group is demonstrated. This practical methodology allows the stereocontrolled synthesis of glucosides with a 1,2-trans linkage.

An efficient protocol for the conversion of silyl enol acetals into δ,δ-bis(aryl) β-keto esters was developed. In the presence of an aromatic nucleophile, activation of the acetal by a catalytic amount of Lewis acid facilitates the disubstitution reaction to afford a series of valuable functionalised β-keto esters.

A new strategy for the synthesis of highly efficient symmetric and asymmetric BODIPY fluorophores that combine trifluoromethyl and 3,5-aryl substituents has been developed. The key step is the P₂O₅-promoted condensation of 2,2,2-trifluoro-1-(5-arylpyrrol-2-yl)-1-ethanols with diverse 2-arylpyrroles.

Substituted phenanthridines, such as the natural product trispheridine, can be accessed by the practical photochemical cyclization of N-benzylanilines, with functionalities tolerated on both the A and C rings. The phenanthridines are accessible in good to very good yields (up to 95 %) from iodinated substrates, whereas brominated substrates perform poorly in comparison (0–48 %).

A 3-O-alkylated aromatic oligoamide foldamer incorporating an additional and hydrophilic 6-O-alkyl substituent in the central monomer is shown to have improved solubility, adopt an active binding conformation and disrupt the p53–hDM2 interaction.

The repeating unit of the O-specific polysaccharide (PS) from Shigella flexneri serotype 6 (SF6) strain MDC 2924-71 has been studied by NMR spectroscopy, confirming a non-stoichiometric O-acetylation at one of the rhamnosyl residues. The synthesis of di- to tetrasaccharide derivatives with and without mono-O-acetylation is reported. Structures are common to SF6, SF6a, and Escherichia coli O147.

The cascade benzannulation-lactonization of phthalides with α-carboxyfurylacrylates was employed as the key reaction for the concise synthesis of neo-tanshinlactone.

The dehydrogenation of perfluoroalkyl ketones by using an oxoammonium salt is reported. The reaction proceeds under mildly basic conditions and affords α,β-unsaturated products in fair to excellent yields. The reaction likely proceeds through a two-step sequence. The spent oxidant can easily be recovered and used to regenerate the oxoammonium salt.

Selenium analogues of isotryptophan and homoisotryptophan derivatives were synthesized by Sonogashira coupling of iodophenyl methyl selenide with alkynyloxazolidines followed by iodocyclization as the key step. Sonogashira coupling of 3-iodobenzoselenophene with ethynyloxazolidine afforded the selenohomotryptophan derivative.

We present the first synthesis and study of N-alkylated ortho-aminomethyl-benzamides termed “ortho-arylopeptoids”. These compounds can be synthesized both on solid-phase and in solution using a unique submonomer method and constitute a rare example of aromatic oligoamides with ortho-connectivity. The tert-butyl and phenyl side chains offer complete control over the amide conformations.

A general access to C-4-substituted Neu5Ac glycals combining elements of molecules showing anti-neuraminidase activity.

A simple chemoenzymatic preparation has been developed for the production of serotonin receptor agonist (R)-Frovatriptan starting from inexpensive starting materials. The enzymatic action towards ketone or alcohol intermediates is the key step for the asymmetric total synthesis of this drug.

α/β-Peptides were synthesized from alternating fused furano-pyran β-amino acid/L-Ala units, and their conformations were analyzed. The system adopted a left-handed 9/11-helix that was supported by 7-mr H-bonding at the N-terminus.

An efficient, copper-mediated cascade synthesis of aryl nitriles from aryl halides using benzyl cyanide as the cyanide source is described. Compared with traditional copper-mediated cyanation reactions, this approach effectively avoided the use of toxic MCN and low soluble reagents. Furthermore, C–H oxidation and C–CN cleavage are proposed to be involved in this cascade process.

Cycloaddition between a carbohydrate-derived nitrone and suitable chemoenzymatically prepared enantioenriched allylic and homoallylic alcohols allowed the straightforward synthesis of three tetrahydroxyindolizidines and one tetrahydroxypyrrolizidine related to natural hyacinthacines B. They inhibit amyloglucosidase from Aspergillus niger and β-glucosidase from almonds.

A range of secondary N-alkylanilines smoothly underwent DDQ-promoted oxidative olefination with 2-alkylazaarenes, acetophenone, and malononitrile to give structurally diverse alkenes in moderate to excellent yields with excellent (E) selectivity. Mechanistically, the reaction proceeds through amine oxidation followed by imine olefination (DDQ = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone).

The reactivity of monoester iodonium ylide is investigated. Highly labile mono ester iodonium ylide generated in situ from β-butoxy-β-acyloxyvinyl-λ³-iodane through an ester exchange reaction cleanly undergoes Darzens-type condensation with aromatic aldehydes to afford trans-epoxy ester selectively.

Complex amine-containing stereotriads are recurring motifs in a number of bioactive and pharmacologically important molecules. The regio- and stereocontrolled aminohydroxylation of bicyclic methylene-aziridines can be followed by carbonyl reduction to deliver 1,3-diamino-2-ols in good yields with good diastereoselectivities (Ts = para-tolylsulfonyl, Bs = phenylsulfonyl, Boc = tert-butoxycarbonyl).

A Beckmann reaction of a porphyrindione monooxime is used to expand a pyrrole to a pyrazine imide moiety within the porphyrin and generate a new pyrrole-modified porphyrin-like compound that contains a six-membered heterocycle. The imide functionality can serve as a synthetic handle for further manipulations of the chromophore.

A new method for the synthesis of both isomers of chiral 1,3-disubstituted allenes with enantiomeric purity up to 99 % ee, using selectively alkylated chiral camphanyl-piperazines, aldehydes, terminal alkynes, and ZnBr₂ has been developed.

A common alkyne-mediated approach to the total syntheses of cladospolides A, B, and C and iso-cladospolide B was accomplished by using an alkyne-zipper reaction, a Sharpless asymmetric epoxidation/dihydroxylation, and a Yamaguchi macrolactonization as the key steps.

Activation energies, distortion energies, and TS conformational data were compared in a set of strained cyclooctynes in strain-promoted azide–alkyne cycloaddition (SPAAC) reactions. Only electronic effects could be accurately related to experimental rate data.

As an efficient route to dithiocarbamates, a simple and versatile method for preparing S- and N-functionalized dithiocarbamates starting for readily available cyclic sulfates and commercial amines under environmentally friendly conditions is reported.

Ionic liquids with the cationic part based on the structure of epibatidine (a 7-azabicyclo[2.2.1] skeleton) have been prepared. The chemical and physical properties of these ionic liquids with dicyanamide and bis(trifluoromethylsulfonyl)imide anions were investigated and they were found to show very good electrochemical and thermal stability.

The regioselective aminoalkylation of indoles and heterocycles with α-amido sulfones under basic conditions is described. The reaction with MeMgBr/MgBr₂ gives 3-(1-carbamoylalkyl)indoles, whereas employing Cs₂CO₃ yields 1-(1-carbamoylalkyl)indoles. The first case presents a switch of the leaving group of the α-amido sulfone, whereas the second demonstrates a switch in the regioselectivity.

Nazarov electrocyclization is a synthetic method for the preparation of functionalized five-membered rings, often in a stereospecific manner. This review highlights innovative strategies for gaining access to the key pentadienyl cation intermediates and illustrates how these new approaches have expanded the scope and utility of the reaction.

A family of functional materials bearing a perylene core and terpyridine branches, along with their Ru^II–bis(terpyridine) complexes, was designed and synthesized. Their structures were elucidated by NMR spectroscopy and MS. Their optical properties showed absorption spectra that ranged from 250 to 625 nm, which suggests their possible use as sensitizers for dye-sensitized solar cells.

Organocatalysis and ring-closing metathesis enable a two-step synthesis of azaheterocyclic vinylphosphonates, giving access to five- and six-membered ring compounds. The required (ω-alkenyl) p-toluenesulfonamides were obtained through the Mitsunobu reaction, which allows the synthesis of chiral phosphonates.

The cancer-cell-cytotoxicity-guided fractionation of the acetone extracts of two cultured marine-derived Streptomyces strains yields six new napyradiomycins (1–6). Napyradiomycins 1–4 are new members of the napyradiomycin “C-type” meroterpenoids, which possess a linear monoterpene bridge between C-7 and C-10a. The cytotoxicity and antibacterial activities of 1–6 are presented.

The synthesis of heterobase-functionalized cyclopentene derivatives as valuable substrates for the introduction of suitable substituents through pericyclic reactions is reported. The structures of ene and 1,3-dipolar adducts are discussed, and the primary antiviral activities of some adenine derivatives are reported.

(E)-2-Cyano-3-(5′-piperidin-1-yl-2,2′-bithien-5-yl)acrylic acid (p-TTCNAc) can be conveniently used as a fluorescent probe to identify prefibrillar oligomers of hen egg white lysozyme not detected by Thioflavin-T (ThT).

Pillar[n]arene (n = 5 or 6) derivatives substituted with peripheral mesogenic moieties gave rise to an enantiotropic smectic A phase over a very broad temperature range, whereas only a monotropic mesophase was observed for the corresponding constitutive acyclic monomeric subunit.

Simple tripeptides are shown to be effective ligands for iridium-catalyzed transfer hydrogenations. Peptide–iridium complexes efficiently reduce ketones, aldehydes, imines, and NAD⁺ under mild conditions in aqueous buffer. As genetically encodable foldamers, peptides are attractive ligands for the construction of artificial metalloenzymes for diverse biotechnological applications.

Donor-activated triple bonds act as substrates for cycloaddition-retroelectrocyclization reactions with TCNE or TCNQ to give cyanobutadienes. Herein we showcase the activation ability of two classes of donors: organic amines and platinum(II) centers directly bound to the acetylenic moieties and compare them directly for the first time.

New molecules derived from cucurbit[6]uril with either a propanediurea unit or cyclohexane moieties have been synthesized. Their solubility in pure water increased with the number of these nonclassical units. This can be explained in terms of changes in intermolecular C–H···O hydrogen bonding rather than in the molecular shape.

The structural characterization of the lipooligosaccharide from the steno-psychrophilic bacterium Colwellia psychrerythraea strain 34H has been achieved by means of chemical analysis, mass spectrometry, and NMR spectroscopy experiments. The data revealed a very short, negatively charged, and unique oligosaccharide, lacking heptose residues.

The first examples of phosphane-catalyzed [3+2] annulation of allenoates to 6-alkylidenepenicillanates leading to chiral spirocyclopentenyl-β-lactams are reported. The process involves the generation of either two or three consecutive stereogenic centers, including a quaternary chiral center.

A simple method for the synthesis of secondary amines starting directly from nitriles by using a ruthenium catalyst is described. With this novel domino system, various nitriles were reduced and subsequently N-monoalkylated in excellent yields (up to 99 %). In addition to isopropanol, other alcohols were also used as a reductant and N-monoalkylation reagent.

New 9-(fluoren-2-yl)anthracene derivatives with combined blue-light-emitting and hole-transporting characteristics have been developed that exist in a stable amorphous state and deliver high fluorescence quantum yields.

A radical C–C bond formation between olefins and alcohols proceeded efficiently by simple light irradiation at room temperature without using the harmful elements often used in conventional radical reactions.

Optical spectroscopic studies of the small, well-folded peptide foldamer, Trp-cage miniprotein. Investigation of stability-associated aggregation properties of three Trp-cage foldamers.

The Zn^II-cyclen macrocycle is revealed to be an efficient and selective molecular probe for tagging thymidine (Td) nucleoside functionalities covalently linked to multiwalled carbon nanotubes (MWCNTs).

Characteristic conformational features of the Ant-Pro reverse turn ― a folded pseudo β-turn motif with a closed nine-membered-ring H-bonded network involving just two amino acid residues ― are described. The results were obtained from the investigation of ten crystal structures and their NMR conformations in the solution state.

An efficient synthesis of 5-organotellanyl-1H-1,2,3-triazole compounds through [3+2] cycloaddition reaction of organic azides and (organotellanyl)alkynes is presented. The 5-organotellanyl-1H-1,2,3-triazoles were readily functionalized at the 5-position to give highly functionalized triazoles.

Three types of peptide oligomers that contain cis-2-aminocyclohexanecarboxylic acid (cis-ACHC) were analyzed by two-dimensional NMR spectroscopy and X-ray crystallography. Folded conformations do not appear to be populated in solution. Crystallographic data reveal extended confomations with specific preferences for cis-ACHC residues.

A method for the trimethylsilyl cyanide (TMSCN) addition to α-fluoro ketones has been developed, giving the nitrile products in high yields and with good to modest stereoselectivities. TMSCN is activated in strongly electron-donating solvents, such as DMF, to produce the fluorinated TMS-protected cyanohydrin in yields of up to 95 % and diastereoselectivities as high as 22:1.

Benzo-fused cyclic sulfamidate heterocycles have been synthesized in 71–97 % yields through a cycloaddition reaction of allenoate with cyclic imines (various aldimines and a trifluoromethyl ketimine) by using PPh₃ as organocatalyst. After screening several commercially available chiral phosphanes, up to 36 % ee was obtained with (R)-H₈-BINAP.

[1,2,4]Triazolo[3,2-c][1,2,4]triazole has three tautomers: 2H, 3H and 5H. It is shown that the most stable tautomer is 2H, tautomer 3H has intermediate energy and the 5H has the highest energy. This compound provides a striking counter-example of the generally held view that the organic conjugated structure with the highest number of alternating single and double bonds is the most stable.

Macrocyclic peptoid oligomers that organize into globally amphiphilic faces show potent antimicrobial activity against clinical isolates of methicillin-resistant Staphylococcus aureus (MRSA) and disrupt the bacterial cell surface, as shown by scanning electron microscopy. Scale bar: 300 nm.

A library of symmetric and unsymmetric singly linked and triply fused porphyrin dimers are synthesized in moderate to very good yields. A variety of functional groups are tolerated. Numerous synthetic strategies, incorporating oxidative radical coupling and organolithium and palladium-catalyzed coupling methods, are utilized.

A one-pot three-component tandem reaction with a subsequent intramolecular hydroamination reaction was applied to generate libraries of benzazepino-indole and isoquinolino-benzazepino-indole derivatives.

Aryl thioethers and selenides were prepared in good yields with high meta regioselectivity through sequential Ir-catalyzed C–H borylation and Cu-promoted C–S and C–Se bond formation in one pot. A wide range of functional groups were tolerated under the reaction conditions. In addition to aryl thiols and selenides, alkyl thiols and selenides were also suitable coupling partners in this reaction.

A new synthetic strategy for nitrogen heterocycles was developed that incorporates fused-ring systems and takes advantage of a stereodefined ring-rearrangement metathesis process of substituted 7-azanorbornenes as the stereocontrolled key step. A set of new 1-azabicyclo[n.3.0]alkenones (n = 3, 4, and 5) that include new analogues of pyrrolam were prepared by using this methodology.

Two carbene-based ligands have been attached to perbenzylated and permethylated cyclodextrins. Their palladium complexes were synthesized, characterized and used as catalysts in Suzuki–Miyaura coupling reactions both in ethanol and water.

Extended but constrained conformations are preferred when a chiral cyclobutane moiety forms part of the backbone in different polycyclobutane γ-peptides. Nevertheless, strong hydrogen bonds promoting folded conformations are produced in hybrid peptides when the carbocycle is not part of the main polyamide skeleton but acts as a chiral branched platform providing functionalized side chains.

The supramolecular multivalency of discotic molecules, which feature either a single or three mannose units and self-assemble into columnar polymers, is evaluated. The binding affinity of the multivalent supramolecular polymers is enhanced compared to that of the monovalent bioactive ligand. Additional decoration with three mannose ligands does not further contribute to the binding.

The discovery of a large-diameter β-peptidic foldamer mixed helix is reported. The formation of the β-H18/20_P helix is solvent- and concentration-dependent, and occurs by a head-to-tail self-assembly process in solution.

A series of dinuclear chloride-binding foldamers have been synthesized from naphthyl- and anthracenyl-decorated, ortho-phenylene-bridged oligoureas (tetrakisurea to hexakisurea).

Short series of terminally protected, fully thioamidated, homo-α-peptides were synthesized. For the first time, their preparation was achieved in single-step fashion through direct thionation of their oxygenated precursors. Conformation analysis confirms that the thioamidated α-amino acid residues can easily adopt either folded or fully extended conformations.

The Masuda borylation/Suzuki arylation sequence furnishes in a concise one-pot manner camalexins and 3,3′-biindoles, compounds that show pronounced antifungal, antimicrobial, and cytotoxic activities.

We describe the synthesis of cyclic γ-amino acids that have a cis relationship between the amino and the carboxylic acid groups. This makes them suitable for the design of foldamers that adopt β-sheet-type structures.

Two analogues of meiogynin A, a natural sesquiterpenoid dimer that interacts with a family of antiapoptotic proteins, were synthesized. They were obtained in only eight steps with very good selectivity, without any protection steps.